Bis(4,4&#39;-diphenylmethyl) bibenzyl-bis (hexachloroantimonate)



United States Patent 3,466,313 BIS[4,4-DIPHENYLMETHYL] BIBENZYL-BIS(HEXACHLOROANTIMONATE) Irving Kuntz, Westfield, and Robert M. Thomas,Mountainside, N.J., assignors to Esso Research and Engineering Company,a corporation of Delaware No Drawing. Original application Apr. 8, 1965,Ser. No. 446,714. Divided and this application Aug. 27, 1968, Ser. No.777,528

Int. Cl. C07f 9/92 US. Cl. 260-446 1 Claim ABSTRACT OF THE DISCLOSUREThis invention relates to bis [4,4'-diphenylmethyl] bibenzyl-bis(hexachloroantimonate) which is useful as a catalyst in polymerizationreactions between tetrahydrofuran and cyclopentadiene alone or in thepresence of an oxirane or oxetane compound.

The present application is a divisional of SN. 446,714 filed Apr. 8,1965.

The present invention relates to new tetrahydrofurancyclopentadienepolymers and a method for their preparation. More particularly, theinvention is directed to copolymers of tetrahydrofuran andcyclopentadiene and also terpolymers of tetrahydrofuran, cyclopentadieneand a third oxirane or oXetane comonomer and to a method for theirpreparation.

Various copolymers of tetrahydrofuran (tetrarnethyleneoxide) with othermaterials have been reported as being prepared with various types ofpolymerization initiators. Moerwein, in German Patent No. 914,438

found that copolymers of tetrahydrofuran with ethylene oxide could beprepared utilizing borontrifluoride or antimony trichloride but notaluminum chloride or zinc chloride polymerization initiators. Most ofthe polymers described as being formed with the catalyst systems of theprior art are characterized as being mobile or viscous liquids.

Now in accordance with this invention, polymer products capable of awide variation in form and utility are prepared by polymerizingtetrahydrofuran with a monomer system made up of either cyclopentadienealone or cyclopentadiene and an oxirane or oxetane compound. Thepolymerization is conveniently conducted at relatively low temperaturesand at mild pressures in the presence of aromatic diluents or in bulkwith a mono or bis dior tri-aryl methyl carbonium ion salt catalyst.Depending upon the proportions of monomers in the final polymercomposition, the products of this invention may be elastomers which canbe vulcanized with sulfur and accelerators, surface coatings which maybe applied from a solvent vehicle to form crosslinked films on airdrying or thermoplastic compositions.

As stated above, the polymers encompassed by the present inventioninclude copolymers of tetrahydrofuran with cyclopentadiene as well asterpolymers of tetrahydrofuran, cyclopentadiene, and an oxirane(1,2-epoxide) or oxetane (1,3-epoxide) compound. The generic formula forthese epoxide compounds may be represented as:

wherein any of R through R is a hydrogen, a C to C alkyl group, a C to Chaloalkyl, a C to C aryl or a C to C ether. Preferably, the value of theRs are C -C alkyls or haloalkyls. The value of n in the above formula isequal to O or 1 and when n is equal to 0 it is necessary that at leasteither R or R be a bydrogen radical. The R groupings may be the same ora different moiety within the limits of the above formula.

Representative non-limiting examples of useful oxirane and oxetanecompounds include ethylene oxide, propylene oxide, epichlorohydrin,trimethylene oxide, styrene oxide, allyl glycidyl ether, 2-phenyloxetane, 3,3-bis (chloromethyl) oxetane, 1,2-dodecane oxide,1,4-cyclohexane oxide, and l,2-epoxy-5,6 trans-9IO-cis-cyclododecadiene.The preferred epoxide compounds are propylene oxide,3,3-bis(chloromethyl) oxetane and allyl glycidyl ether.

The present polymerization process may be carried out in bulk such as inan excess of tetrahydrofuran. Additionally, solvent polymerizationtechniques may also be used. Aromatic hydrocarbons that are liquid atthe conditions of temperature and pressure used in the polymerizationreaction are preferred for use in the pocess of this invention.Repesentative examples of suitable solvents include benzene, toluene,ethylbenzene, xylene, nitrobenzene, and the like. Mixtures of aromaticsolvents with alicyclic solvents, for example, toluene and cyclohexane,may be used. Halogenated materials such as methyl chloride or methylenechloride should be avoided.

The catalyst system employed in preparing the copolymers and terpolymersof this inventioncomprises at least one dior tri-arylmethyl carboniumion salt. Mono or his carbonium ion salts are effective catalysts. Thegeneral structure of the desired carbonium ion salt may be representedby the following formula:

wherein Ar is a phenyl or naphthyl group or an alkylsubstituted phenylor naphthyl group. Each of the Ar groups may be the same or a differentaromatic moiety. The value of M in the above formula is a cation whichmay be selected from the group consisting of antimony, tin, aluminum,boron, zinc, iron, titanium, zirconium, vanadium and galenium. The valueof x represents a common halide having an atomic number of less than 53, ie chlorine, bromine, fluorine, or a mixture of the same. The valueof x is an integer of from 2 to 3; the sum of x and y must be equal to3; z is equal to the highest valence of the cation M+1; a is an integerof from 0 to 1 and When a equals 0, R is hydrogen and when a is equal to1, R is an ethylene group (C H Representative examples of usefularylmethyl carbonium ion salt catalyst include triphenylmethyl antimonyhexachlordie (triphenylmethyl hexachloroantimonate), triphenylmethylaluminum tetrachloride, triphenylmethyl tin pentachloride,triphenylmethyl boron tetrachloride, triphenylmethyl borontetrafiuoride, triphenylmethyl diethyl aluminum dichloride,triphenylmethyl-chloro-boron trifluoride, triphenylmethyl-bromo-antimonypentachloride, diphenylmethyl antimony hexachloride, bis[4,4'-diphenylmethyl] bibenzyl-bis (hexachloroantimonate etc. The preferredaryl group in the carbonium ion catalyst is a phenyl radical and thepreferred cation is antimony. The most preferred salt is triphenylmethylantimony hexachloride. The total amount of catalyst employed in thepolymerization reaction varies with the choice of monomers to bepolymerized and the choice of components of the cat- ,alyst system, butis generally in the range of from about 0.005 to 0.2 mole of catalystper 100 moles of monomers.

The conditions at which the polymerization reaction is conducted canvary over a wide range. Generally, temperatures ranging from to 50 C.can be used; however, temperatures ranging from 30 to 30 C. arepreferred. The pressure at which the polymerization is carried out isnot critical and pressures ranging from 0.2 to 1000 p.s.i.g. can beemployed in the polymerization reaction. Pressures in the range of fromabout 1 atmosphere to 10 atmospheres are most generally used. Thereaction time used in the formation of the preferred copolymers andterpolymers depends in general upon the temperatures used. Generally,reaction times can vary from minutes to weeks; however, it is more usualto use reaction times ranging from about 0.25 to 100 hours.

The reaction vessel can be constructed of any material that is inert tothe reactants and diluents used, and is capable of withstanding theoperating pressures. Reaction vessels made of glass, stainless steel andglass-lined steel are satisfactory.

In a typical polymerization procedure, a glass reaction vessel ischarged with benzene and a catalytic amount of triphenylrnethyltetrafluoroborate. To this mixture of catalyst and solvent is thenintroduced a monomer mixture consisting of tetrahydrofuran,cyclopentadiene and trimethylene oxide. In general, about 0.005 to 0.2mole of catalyst is used per 100 moles of monomer. The glass reactionvessel containing the reaction mixture is then sealed and placed in aconstant temperature bath, maintained at a temperature ranging from 30to +30 C. The reaction vessel and its contents are continuously tumbledin the constant temperature bath during the period of reaction. Polymerisolation and catalyst removal can be achieved utilizing a variety oftechniques. In one procedure, the polymer solution is introduced intoexcess non-solvent such as methanol or water to precipitate the polymer.Prior to precipitation the polymer solution can be washed with aqueousacid or base to effectively remove and deactivate catalyst residues. Ifdesired, additives and stabilizers may be introduced into the polymersolution prior to precipitation. An especially attractive finishingprocess involves the introduction of the polymer solution into a body ofhot water containing acidic or basic deashing agents and whateveradditives or stabilizers as may be desired.

The copolymer and terpolymer products of the present invention asprocured by the above process exhibit molecular weights ranging fromabout 500 to l,000,000. Molecular weight determinations in the case ofhigh molecular weight polymers is secured by membrane osmom metry or inthe case of lower molecular weight materials by vapor phase osmornmetry.The copolymer and terpolymer products exhibit intrinsic viscositiesranging from about 0.05 to 5.0 as determined in benzene at of silicon,aluminum, magnesium, titanium, or the silicates or aluminates of thevarious elements indicated may be compounded with the elastomericproducts of the present invention.

Polymers containing more than about 30 mole percent cyclopentadieneresidues tend to be thermoplastic materials. Such polymers may be moldedand pressed or cast into films. Lower molecular weight products of thistype are especially useful as components for varnish and paintformulations although the more insoluble high molecular weight productscan be used. These polymer products air-dry to a hard, tackfree surface.The elastomeric products of this invention may be utilized in thepreparation of tires, inner tubes, hose and tubing, wire and cablecoatings, mechanical goods, as well as for a wide variety of coated andmolded articles.

This invention and its advantages will be better understood by referenceto the following examples:

Example 1 A series of polymerization tests were conducted to illustratethe effectiveness of the catalyst system of the present invention forthe copolymerization of tetrahydrofuran and cyclopentadiene. In everyinstance, the test was carried out in a sealed glass reaction vessel.The reaction system was made up of dimer-free cyclopentadiene,tetrahydrofuran and a triphenylmethyl hexachloroantimonate catalyst inthe amounts specified in each of the runs. The polymerization wasconducted in bulk at a temperature of 7 C. for a period of 72 hours.After the completion of the polymerization reaction the total reactionmixture was poured into excess methanol to precipitate the polymerproduct. The polymer product thus obtained was then vacuum oven driedand tests were conducted to determine the polymer inherent vis cosityand polymer structure. Inherent viscosity measurements were made inbenzene solution at 25 C. Copolymer structure, i.e. the amount ofcyclopentadiene and tetrahydrofuran present in the polymer, wasdetermined by nuclear magnetic resonance measurements of 10% solutionsin carbon tetrachloride. The results of the tests are set forth in TableI below:

TABLE I Feed Polymer Inherent CPD 1 THF 9 Mole percent Catalyst Yieldviscosity Molepercont Mole percent B n (ml.) (ml) CPD 1 (mg.) (gr.)(avg.) CPD I THE 3 I cyclopentadiene. 2 Tetrahydroturan.

a temperature of 25 C. at a polymer concentration of from 0.05 to 0.50gram of polymer per 100 cc. of solu tion. The polymers produced aresoluble in tetrahydrofuran, benzene, chloroform, toluene, cyclohexane,and methylene chloride.

The copolymers and terpolymers of this invention can be designed fordifferent end uses. The high molecular weight polymers containing atleast about 75 mole percent tetrahydrofuran residues with the remaining25% of the composition being either cyclopentadiene or cyclopentadieneand an oxirane or oxetane compound residues are highly usefulelastomers. The products may be vulcanized by using sulfur andaccelerators such as 2-benzothiazyl disulfide, mercaptobenzothiazole,cyclohexyl-2-benzothiazyl sulfenamide, telluriuim diethyldithiocarbamate, etc. Carbon blacks such as the channel blacks, furnaceblacks and thermal blacks and/ or mineral fillers such as the oxides,hydroxides, carbonates, etc.

The above tests indicate that copolymers of tetrahydrofuran andcyclopentadiene containing various amounts of each of the monomers arereadily formed with the catalyst system of the present invention. Thepolymers thus formed contain varied amounts of unsaturation.

The polymer described in Run 4 of Table I was formulated as a solutioncontaining 50% solids in toluene for testing as a varnish. It wasapplied to a carbon steel panel and air-dried to a tack-free finish intwo hours. After drying for a total period of five hours at roomtemperature, the film exhibited an H hardness in a pencilhardness test.

Example 2 A further series of tests were conducted to demonstrate theeffectiveness of the catalyst system of the present invention for theterpolymerization of tetrahydrofuran, cyclopentadiene, and an epoxidecompound. Each test was carried out in a 30 ml. glass reaction vesselusing 40 mgs. of triphenylmethyl hexachloroantimonate. Thepolymerization was conducted in bulk at a temperature of 7 C. for aperiod of 40 hours. The amounts of monomers used in the formation of thepolymer are set forth in the table. Inherent viscosity measurements andthe percentage of epoxide compound present in the polymer using infraredspectroscopy were determined. The results of the tests are set forth inTable II below:

weight stearic acid, 5 parts by weight zinc oxide, 2 parts by weightwhite lead, 2 parts by weight sulfur, 1 part by weight (Altax)benzothiazyl disulfide, and 1.5 parts by weight (Tuads) tetramethylthiuram disulfide. The total composition was then cured into a pad at300 F. for a period of 60 minutes. The pad was subsequently cut into astandard dumbbell and tested under ASTM conditions of temperature andhumidity on a Scott Micro-Tensile TABLE II Feed Terpolymer CPD 1 AGE 2THF 5 Inherent Mole percent (1111.) (1111.) (m1.) Yield (gr.) viscosityAGE 2 l Cyclopentadiene. 2 Allyl glycidyl other. 3 Tetrahydroturan.

During the course of the terpolymerization a transient blue color of thepolymerization solution was observed. This blue color was also producedduring the copolymerization of tetra'hydrofuran with cyclopentadiene.This observation indicates that the small amounts of cyclopentadienepresent were tel-polymerized in the experiments set forth in Table IIwith the catalyst system of the present invention. The polymers obtainedcontained minor amounts of unsaturation and are readily vulcanized tosolvent and oil-resistant vulcanizates.

Example 3 An additional series of tests were conducted to demonstratethe flexibility possible with the process of this invention by thepreparation of terpolymers of tetrahydrofuran, cyclopentadiene and athird oxirane or oxetane comonomer. Each test was carried out in a 30ml. glass reaction vessel using amounts oftriphenylmethylhexachloroantimonate catalyst specified in each of theruns. Polymerizations for all charges were carried out in bulk at atemperature of 7 C. for 45 hours. The amounts of monomers used in theformation of the polymers are set forth in the table. Polymer productswere isolated from the reaction solution by precipitation into methanol.All products were insoluble in this solvent except the product from Run3 Where the amounts of propylene oxide residues in the terpolymer weresufiicient to lead to solubility in methanol. In this instance thepolymer product was isolated by evaporating the reaction solvent and themethanol from the product. The results of the tests are set forth inTable III below:

Tester. The cured sample exhibited a tensile strength of 1330 psi. andan elongation at break of 350%. The modulus at 300% extension was 1250p.s.i.

The cured polymers of the present invention also exhibit solvent and oilresistant properties. For example, the weight percent increase of theabove cured terpolymer in ASTM No. 3 oil at 100 C. was 146%.Styrene-butadiene rubber or butyl rubber vulcanizates, with similarproportions of fillers, illustrate a weight percent increase rangingfrom 300 to 400%, or even more, in the same test. The room temperatureweight percent increase in ASTM No. 3 oil of the cured terpolymers ofthis invention was 24%; a vulcanizate of Neoprene W, a well-known,oil-resistant elastomer, showed a 34% weight increase in the same test.

Example Bis[4,4 diphenylmethyl1bibenzyl bis(hexachloroantimonate) wasprepared by reacting 0.5 gram of 4,4- bis(chlorodiphenylmethyl)bibenzylin 20 ml. of carbon tetrachloride with two times the theoretical amountof SbCl Upon mixing, a brown salt immediately precipitated. This productwas recrystallized from a mixture of carbon tetrachloride and methylenechloride and analyzed for carbon, hydrogen and chlorine content.

The desired product has an empirical formula of C H Cl Sb with acalculated carbon content of 40.65 wt. percent, a hydrogen content of2.73 wt. percent and a chlorine content of 36.01 wt. percent. Theanalysis revealed a carbon content of 40.94 wt. percent, a hydrogencontent of 2.74 wt. percent and a chlorine content of 35.96 wt. percent.

TABLE III atalyst Yield Inherent THF 1 CPD 2 PO 3 BCMO 4 (mg) (gin)viscosity 6 1 Tetrahydrofuran.

2 cyclopentadiene.

3 Propylene oxide.

4 3,3-bis (chloromethyl) oxetane.

5 Determined in benzene at 25 C.

To demonstrate the curability of certain types of the polymers formedwith the catalyst system of the present invention, 100 parts by weightof the polymer of Run 1 of Table II was compounded on a rubber roll millwith parts by weight of high abrasion furnace black, 1 part by weight ofphenyl-B-naphthylamine, 1 part by weight of (PX-441) 2,6-ditertiarybutyl-p-cresol, 2 parts by A mixture consisting of 2 ml. cyclopentadieneand 18 ml. of tetrahydrofuran is polymerized with a 40 mg. portion ofthe bis carbonium ion salt prepared above at a temperature of 7 C. for72 hours. The resulting polymer is an elastomeric substance that isreadily cured with sulfur and conventional accelerators.

Further advantages of this invention will be apparent to those skilledin the art. Polymers of tetrahydrofuran, cyclopentadiene and an epoxidecompound can be prepared with the process of the present invention. Itis to be understood that this invention is not limited to the specificexamples set forth herein, which have been offered merely asillustrations, and that modifications may be made without departing fromthe spirit and scope of the appended claim.

What is claimed is:

1. Bis[4,4' diphenylmethy1]bibenzylbis (hexachloroantimonate) 3,328,4456/1967 Harrison 260-440 3,251,881 5/1966 Susi et a1 260446 X TOBIAS E.LEVOW, Primary Examiner References Cited UNITED STATES PATENTS 5 W. F.W. BELLAMY, Assistant Examiner Harrison 260-4 US. Cl. X.R.

Harrison 260-440 Harrison 260 440 252-431; 260-429.7, 448, 606.5, 429.9,439, 429.5, Harrison 260 44O 10 429.3, 429

